Pad bath formulation of iron salt,potassium permanganate,ammonium oxalate and zirconyl ammonium carbonate

ABSTRACT

ORANGE TO BROWN MINERAL DYEINGS ARE CONVENTIONALLY PREPARED FROM TWO BATH SYSTEMS, WHERE THE FABRIC IS WETTED WITH ONE BATH CONTAINING AN IRON SALT, AND THEN WETTED WITH ANOTHER BATH CONTAINING ALKALI, TO CAUSE THE COLORED IRON OXIDE TO DEPOSIT IN THE FABRIC AS A MINERAL DYE. THIS HAS BEEN NECCESSARY UP TO NOW, SINCE IT HAS BEEN CHEMICALLY INCOMPATIBLE TO HAVE THE IRON IN THE SAME ALKALINE BATH WITH THE ALKALI. THIS INVENTION DEMONSTRATES THAT A HEAT DECOMPOSABLE COMPLEX OF THE IRON, WITH OR WITHOUT MANGANESE, CAN BE COMPATIBLE WITH ALKALINE ZIRCONYL AMMONIUM CARBONATE SOLUTIONS IN THE SAME BATH, WHEN CELLULOSICS CAN BE WETTED IN THIS BATH, AND SUBSEQUENTLY MINERAL DYED BY HEAT CURING, WHEN THE COMPLEX OF IRON DECOMPOSES TO DEPOSIT IRON OXIDE WITH ZIRCONIA, THE ZIRCONYL AMMONIUM CARBONATE DECOMPOSING AT THE SAME TIME TO DEPOSIT ZIRCONIA. WHEN HEPTAVALENT MANGANESE (KMNO4) IS INCORPORATED INTO THE BATH WITH THE COMPLEXED IRON, IT IS SOLUBLE AND COMPATIBLE, PRODUCING MANGANESE DIOXIDE (MNO2) BY REDUCTION PRODUCTS FROM THE IRON COMPLEX RESULTING IN VARIOUS SHADES OR ORANGE TO BROWN WITH THE IRON OXIDE AND ZIRCONIA ALSO DEPOSITED. THIS PROCESS MAKES IT POSSIBLE TO DEPOSIT ORANGE TO BROWN WASH-FAST MINERAL DYEINGS FROM A SINGLE BATH. THE DEPOSITED ZIRCONIA ATTRIBUTES A DEGREE OF WATER REPELLENCY AND ALGAECIDAL RESISTANCE TO THE FABRIC, AND A COPPER OR PHENYL-MERCURY SALT CAN BE INCORPORATED INTO THE ZIRCONYL AMMONIUM CARBONATE COMPONENT OF THE SYSTEM TO DEPOSIT A FUNGICIDAL MINERAL DYE OF ORANGE TO BROWN SHADE ON HEAT CURING, MAKING IT POSSIBLE TO APPLY AN IRON AND/OR MANGANESE MINERAL DYE WITH OR WITHOUT FUNGICIDE FROM A SINGLE BATH, REDUCING CONVENTIONAL DYEING PROCEDURES FROM TWO OR MORE BATHS, TO A SINGLE BATH REQUIRING ONLY A SIMPLE PAD, DRY, AND CURE PROCEDURE TO EFFECT THE DYEING. THE FABRICS ARE NOT SERIOUSLY TENDERED, AND THE RESIDUAL BY-PRODUCT SALTS MAY OR MAY NOT BE REMOVED BY WASHING, SINCE THE FABRIC IS NOT STIFFENED BY THEIR PRESENCE AND THE DYED COLORS ARE UNAFFECTED ON STANDING.

United States Patent O 3,705,004 PAD BATH FORMULATION OF IRON SALT,POTASSIUM PERMANGANATE, AMMONIUM OXALATE AND ZIRCONYL AMMONIUM CARBONATECharles J. Conner, Metairie, La., assignor to the United States ofAmerica as represented by the Secretary of Agriculture No Drawing.Original application May 19, 1970, Ser. No. 38,900, now Patent No.3,671,178. Divided and this application Mar. 21, 1972, Ser. No. 236,590

Int. Cl. C09b 61 /100 US. Cl. 852 3 Claims ABSTRACT OF THE DISCLOSUREOrange to brown mineral dyeings are conventionally prepared from twobath systems, where the fabric is wetted with one bath containing aniron salt, and then wetted with another bath containing alkali, to causethe colored iron oxide to deposit in the fabric as a mineral dye. Thishas been necessary up to now, since it has been chemically incompatibleto have the iron in the same alkaline bath with the alkali. Thisinvention demonstrates that a heat decomposable complex of the iron,with or without manganese, can be compatible with alkaline zirconylammonium carbonate solutions in the same bath, when cellulosics can bewetted in this bath, and subsequently mineral dyed by heat curing, whenthe complex of iron decomposes to deposit iron oxide with zirconia, thezirconyl ammonium carbonate decomposing at the same time to depositzirconia. When heptavalent manganese (KMnO is incorporated into the bathwith the complexed iron, it is soluble and compatible, producingmanganese dioxide (MnO by reduction products from the iron complex,resulting in various shades or orange to brown with the iron oxide andzirconia also deposited. This process makes it possible to depositorange to brown wash-fast mineral dyeings from a single bath. Thedeposited zirconia attributes a degree of water repellency andalgaecidal resistance to the fabric, and a copper or phenyl-mercury saltcan be incorporated into the zirconyl ammonium carbonate component ofthe system to deposit a fungicidal mineral dye of orange to brown shadeon heat curing, making it possible to apply an iron and/or manganesemineral dye with or without fungicide from a single bath, reducingconventional dyeing procedures from two or more baths, to a single bathrequiring only a simple pad, dry, and cure procedure to effect thedyeing. The fabrics are not seriously tendered, and the residualby-product salts may or may not be removed by washing, since the fabricis not stiffened by their presence and the dyed colors are unaffected onstanding.

This is a division of application Ser. No. 38,900, filed May 19, 1970,now US. Pat. 3,671,178.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedState Government, with the power to grant sublicenses for such purposes,is hereby granted to the Government of the United States of America.

This invention relates to a process for imparting to cellulosicmaterials an orange to brown mineral dyeing with resistance to washingand biological degradation. Specifically, this invention relates to aprocess for imparting to cellulosic materials, through a single bathapplication, an orange to brown series of mineral dyed color shades withresistance to actinic degradation with or without resistance tobiological degradation. More specifically, the invention relates to theformation and subsequent in situ deposition of complex mineral depositsderived from iron, manganese, and zirconium, with or ice Without copperand mercury, in cellulosic materials, to produce mineral dyeings andfungicidal mineral dyeings of said cellulosic materials for the purposeof producing new shades of orange to brown mineral dyeings by reducedprocessing procedures, resistant to actinic degradation, water washing,and biological degradation Among the great number of useful items whichcan be fabricated from the materials treated by the process of thepresent invention are: awnings, tents, tarpaulins, beach umbrellas, shoeliners, life raft covers, sails, cording material, tobacco shade cloth,curtains, camouflage fabrics, etc.

The prior art teaches the application of iron based mineral dyeings bydouble decomposition wherein several baths and washings are commonlyrequired to obtain the desired finish. In addition, the application offungicides required separate pad-dry-cure procedures, separate from themineral dyeings. By the method which is the present invention, arevolutionary chemical mechanism is neces sitated wherein a ferric saltis complexed in an aqueous solution of ammonium oxalate and mixed withzirconyl ammonium carbonate aqueous solution, which become compatible,in solution, with soluble ferric salt-ammonium oxalate alkalinecomplexes so produced. Potassium permanganate is also soluble in thismedium (alkaline) without decomposition, making it possible toincorporate variable amounts of manganese with the iron to producevarious shades of orange to brown mineral dyeings on heat decompositionof the bath on cellulosic fabrics. When a phenylmercuric salt (acetate,lactate, propionate) is dissolved in the zirconyl ammonium carbonate,prior to incorporation into the dye bath, a fungicidal component isintroduced into the bath, which is deposited with zirconia on heatdecomposition (reference US. Pat. No. 3,291,- 635).

Particularly attractive colorations in an orange to brown color rangeare obtained in the cellulosic final products of the present invention.Some of these color shades are in a comparable range with commercialshades now on the market. A significant feature of the present inventionis the ability to impart orange to brown iron based mineral dyeings withand without fungicide by in situ deposition from a water soluble singlebath system, by a simple wet pad and dry-cure procedure.

The main object of this invention is to provide a single bath process toimpart color shades of mineral orange to brown, with or withoutfungicide, by means of simple pad and cure procedures.

A second object of this invention is to produce desired color shades oforange to brown by reducing the need for excessive investment inequipment by reducing the stages or the number of baths which have beencommonly employed in the current industrial processing for iron basedorange to brown mineral dyeings.

A third object of this invention is to provide a process which requiresless chemical and processing controls than those now commonly employedin the art.

In general, this present invention can best be described as a processfor imparting to cellulosic textiles a mineral dyeing consisting ofvarious proportions of iron, manganese, and zirconium oxides with andwithout copper and for phenylmercury Zirconium fungicides, wherein thecombined properties are obtained upon submitting the untreated textileto a single-bath application, comprising:

(a) impregnating a cellulosic textile with a solution containing from 1%to 6% ammonium oxalate and zirconyl ammonium carbonate solution (10% ZrOfrom 10% to 20%, along with 1% to 4% either ferric sulfate [Fe (SO -XHO] or ferric chloride ('FeCl 6H O) with or without 0.5 to 3.7% potassiumpermanganate (KMnO where all of the lower percentages are formulatedtogether for a minimum, and all of the highest percentages areformulated together for a maximum level; or 5 (b) impregnating acellulosic textile with a solution containing 1% to 6.0% ammoniumoxalate and 10% to 16% zirconyl ammonium carbonate solution (10% ZrOwith either 0.5% to 3.7% potassium permanganate (KMnO or 1% to 4% eitherferric chloride (FeCl '6H O) or ferric sulphate where the lowestpercentages are formulated together for a minimum range, and the miximumrange constitutes formulating with the highest percentages;

(c) impregnating a cellulosic textile with solutions of (a) withoutpermanganate, or (b) without permanganate where the 10% to 20% zirconylammonium carbonate solution (10% ZrO contains from 0.2% to 0.6% mercuryas metal, as represented by phenyl mercuric acetate, lactate, orpropionate; or

(d) impregnating a cellulosic textile with solutions of (a) or (b) withor without permanganate, where the 10% to 20% zirconyl ammoniumcarbonate solution (10% ZrO contains from 0.4% to 1.0% copper as metal,as represented by copper metaborate or copper carbonate;

(e) removing the excess solution from the impregnated cellulosicmaterial to obtain about from 50% to 80% wet pickup,

(f) drying the wet, impregnated cellulosic material for about from 4 to8 minutes of time, at temperatures about from 60 C. to 100 C., using thelonger drying times with the lower temperatures, and

(g) curing the dry, impregnated cellulosic material for about from 1minute to 2 minutes at temperatures about from 100 C. to 105 C., usingthe longer curing times with the lower temperatures; or

(h) dry-curing the wetted sample at 100 C. for 6 minutes, or 60 C. for10 minutes.

The incompatability of ferric salts with alkali is known in theliterature. Consequently, ferric oxide pigments have been deposited froma two-bath system in conventional iron based mineral dyeings:

FeCla 3NaOH 1 bath 2nd bath Fe(OH)al +3NaCl deep orange soluble complexF6z(CO3)3l 2(NI'I-l)2 204 HO-Zr'NH.1(C1O4)1J,

orange basic zirconyl 10 ammonium oxalate A F02) O3); F0303 30 OzTorange 7 5 When permanganate is incorporated into the formulation, themanganese reduction by theory follows:

A smmpozol 211M110, 81120 2Mn(OH)zl K200; 10NHaT 90021 111120 brownreddish brown pigment Consequently, when the permanganate is mixed withthe ferric salt in ammonium oxalate, the K CO byproduct acts as an acidacceptor during the cure, along with zirconia from the decomposition ofthe zirconyl ammonium carbonate.

It should be noted that ammonium salts and complexes with iron areresponsible for inhibited iron hydroxide precipitation in the alkaline(pH 8.5 to 9.0) bath, and that the subsequent heat decomposition of theammonium compounds, with loss of ammonia, activates the reduc tion ofpermanganate and precipitation of iron (ic) oxide, along with zirconia(ZrO from the decomposition of zirconyl ammonium carbonate. In theformulation of a pad bath with ferric chloride or sulphate, ammoniumoxalate, and zirconyl ammonium carbonate, the iron is held in solutionby water soluble complex formations (brownish-yellow solutions), wherethe pH is as high as 9.0 and well on the alkaline ammoniacal side of thepH scale. Zirconyl ammonium carbonate creates the necessary bathalkalinity, and is compatible in solution with the iron and manganese inthe padding bath. Also, the zirconyl ammonium carbonate solubilizescopper metaborate, copper carbonate, and phenylmercury salts, producingwater soluble complexes, which are compatible with the dye bath wherethe copper-zirconium is compatible with all baths of manganese and/ oriron, but the phenylmercuric salt-zirconium is only compatible with themanganese fall iron baths. On heat decomposition, these fungicidesproduce practically insoluble residues with zirconia and the iron and/or manganese oxides, to produce fungicidal mineral dyeings incellulosics (U.S. =Pat. No. 3,291,635).

'EXAMPLE 1 Demonstrates the decomposition of potassium permanganate oncellulosics by heat catalysis, The following formulation was prepared:

A sample of scoured duck 8" x 9" was wetted with the bath and allowed toair dry at room temperature (25 (1.). The purple colored fabric slowlydeposited brown manganese dioxide (hydrated) over a period of 1 hour,and no purple permanganate remained unreduced at that time. A secondsample of scoured duck 8" x 9 was wetted with the bath, blotted free ofexcess liquid, and oven dried at C. for 10 minutes. A complete reductionof permanganate resulted in a manganese oxide brown mineral dyeing,demonstrating the complete reduction (chemical) by heat catalysis. Athird sample of duck 8" X 9" was wetted with the bath, blotted free ofexcess liquid, and oven dried at C. for 6 minutes. Complete reduction toa manganese oxide brown mineral dyeing resulted in all instances.However, the higher temperature cure (100 C.) produced a diiference incolor shade, being more golden brown than the sample cured at 60 C. Thisdemonstrates one of the component reactions occurring in the single dyebaths where potassium permanganate is one of the ingredients.

EXAMPLE 2 Demonstrates the reaction and effect of depositing manganesebrown mineral dyeings with zirconia (ZrO- Potassium permanganate (KMnO1.00

Water (distilled) 26.00 Zirconyl ammonium carbonate solution (10% ZrO5.00

Dye bath for Reddish-brown (1% Mn) 32.00

EXAM PLE 3 Demonstrates accelerated heat decomposition of potassiumpermanganate with ammonium oxalate, where the potassium ion issutficiently present to react with oxalic acid as byproduct.

G. Potassium permanganate (KMnO 1.00 Ammonium oxalate (NI-I C O -H O0.50 Water (distilled) 30.50

Dye bath for Manganese Brown (1% Mn) 32.00

A clear deep purple dye bath resulted. A sample of scoured duck 8" x 9"was wetted with the bath, blotted free of excess, and oven-dry-cured at100 C. for 6 minutes A manganese (oxide) brown mineral dyeing resultedwithout severe fabric degradation, as a result of suitable potassiumcontent for the oxalic acid byproduct. Some degradation occurs frompermanganate oxidation.

EXAMPLE 4 Demonstrates fabric degradation or tendering where the oxalicacid exceeds the potassium content of the bath.

G. Potassium permanganate (KMnO 1.00 Ammonium oxalate (NH C O -H O 1.00Water (distilled) 30.00

Dye bath for Manganese Brown 32.00

A clear deep purple dye bath resulted. A sample of scoured duck 8" X 9"was wetted with the bath, blotted free of excess liquid, and ovendry-cured at 100 C. for 6 minutes. A manganese brown mineral dyed fabricresulted. Some fabric degradation was evidenced by hand tearing, andtensile breaking strength was reduced approximately 40% [EXAMPLEDemonstrates the effect of zirconia deposition with manganese oxidebrown and ammonium oxalate with sufficient potassium and zirconia forbyproduct oxalic acid.

A clear deep purple dye bath resulted. A sample of scoured duck 8" x 9"was wetted with the bath, blotted free of excess liquid, and ovendry-cured at 100 C. for 6 minutes. A uniform reddish-brown mineraldyeing resulted, with some evidence of fabric degradation by hand 6breaking and tearing. The sample was hot tap water washed for 10 minutesat 55 C. without loss of color, and the deposits were stable to waterwashing. Degradation results from permanganate oxidation.

EXAMPLE 6 Demonstrates an iron oxide orange single bath aqueous complexwith Zirconyl ammonium carbonate solution, for mineral dyeing a brightorange shade of color. The following formulation was prepared(5993-124-V):

Ferric sulphate (Fe (SO -xH 'O) 2.00 Ammonium oxalate ((NH C O -H O)3.00

Water (distilled) 40.00 Zirconyl ammonium carbonate solution (10% ZrO5.00

Bright orange dye bath 50.00

A clear coffee colored bath resulted. A section of scoured duck 8" X 9"was wetted with the bath, blotted free of excess liquid, and oven driedat 60 C. for 8 minutes, followed by an oven cure of 100 C. for 2minutes. A bright orange ferric oxide colored mineral dyed fabricresulted. No evidence of tendering could be detected by hand breaking,and tensile breaking strength showed retained fabric strength aftercure, and no oxidative dagradation occurs.

EXAMPLE 7 Demonstrates an iron oxide orange single pad bath system ofcomplexed iron in aqueous solution with zirconyl ammonium carbonate,using ferric chloride as an iron source (5993-l24-VII).

A clear coffee colored bath resulted. A sample of scoured duck 8"x9" waswetted with the bath, blotted free of excess liquid, and oven cured atC. for 6 minutes. A uniform deep bright orange mineral dyed fabric wasproduced. The hand was soft, and no evidence of fabric degradation couldbe detected by hand breaking. A section of the cured treated fabric washot tap water washed for 10 minutes at 55 C., followed by an oven dryingat 130 C. for 2 minutes. No loss of mineral dye could be detected, andthe bright orange color was uniform and comparable with the unwashedsample. Hand was as soft as untreated duck.

EXAMPLE 8 Demonstrates a combination of high iron and low manganese inthe same single bath to produce a brownishorange color shade (5993--IV).

A clear deep purplish-brown bath resulted, with both iron and manganesein solution. A section of scoured duck 8" x 9" was wetted with the bath,blotted free of excess liquid, and oven dried at 60 C. for 8 minutes,followed by oven curing at 100 C. for 2 minutes. A brownishorangemineral dyed fabric was produced, the manganese shading the orange tothe brown side in color. The dyed fabric retained between 89% and 901%retained strength (tensile), and was not adversely affected by hot tapwater washing (55 C.) for 10 minutes, followed by oven drying at 130 C.for 3 minutes. Reduction in permanganate reduced oxidative degradation.

EXAMPLE 9 Demonstrates a combination of high manganese and low iron inthe same single bath to produce an orangebrown mineral dyed fabric(5993-136III).

Potassium permanganate ('KMnO 1.00 Ferric sulphate (Fe (SO xH 0.25Ammonium oxalate (NH C O -H O 0.50

Water (distilled) 43.25 Zirconyl ammonium carbonate solution (10% ZrO 5.00

Orange-brown mineral dye bath 50.00

A clear deep purple bath solution resulted. A section of scoured duck 8"x 9" was wetted with the bath, blotted free of excess liquid, and ovendry-cured at 100 C. for 6 minutes. An orange-brown miner-a1 dyed fabricresulted. The treated fabric was strong and showed high tensile strengthby hand breaking. The sample was hot tap water washed for minutes at 55C., followed by oven drying at 130 C. for 3 minutes. The mineral dyeingwas stable to hot water washing.

EXAMPLE 10 Demonstrates a combination of equal iron and manganese toproduce tan mineral dyeings from a single bath (5993-125-1).

Potassium permanganate (KMnO 0.50 Ferric sulphate (Fe (SO -xH O) 0.50Ammonium oxalate (NH C O -H O 0.50 Water (distilled) 43.50 Zirconylammonium carbonate solution (10% ZrO 5.00

Light tan mineral dye bath 50.00

A deep purple colored clear bath resulted. A section of scoured duck 8"x9" was wetted with the bath, blotted free of excess liquid, and ovendry-cured at 100 C. for 6 minutes. A light tan mineral dyeing resulted.

EXAMPLE 1 1 Preparation of Stock (A) copper metaborate-Zirconyl ammoniumcarbonate and (B) phenylmercuric acetatezirconyl ammonium carbonateaqueous solution for mineral dye bath additions:

Stock solution containing 3.2% copper as metal and 9.0% zirconia (ZrOWhen 5 g. (parts) of this stock are formulated into the mineral dyebaths, 0.16 g. of copper and 0.45 g. of ZrO are introduced into the dyebath in solution.

:Phenylmercuric acetate powder 7.00 Zirconyl ammonium carbonate solution(10% Z'rO 91.00 Ammonium hydroxide (29.5% NH 2.00

Phenylmercuric acetate-Zirconyl ammonium carbonate 100.00

EXAMPLE 12 Demonstrates fungicidal mineral dyeing a reddishbrown withmanganese, copper, and zirconium in a single bath system. Since coppermetaborate-Zirconyl ammonium carbonate (A) stock was found to becompletely compatible with manganesezirconium single bath mineral dyeingsystems, in any proportion, the following bath was prepared and appliedto scoured duck:

Potassium permanganate (KMnO 1.00 Water (distilled) 25.50

Ammonium oxalate (NH C O -H O 0.50 Zirconyl ammonium carbonate-Cumetaborate Clear (reddish-brown) purple dye bath 32.00

A clear purple solution of the bath resulted, containing 0.5% copper(Cu) metal with 0.46% zirconium as ZrO A section of scoured duck waswetted with the bath, blotted free of excess liquid, and oven cured atC. for 6 minutes. A deep reddish brown fungicidal copperzirconiummineral dyed fabric was produced. The dyeing was subjected to 10 minutehot tap water washing, followed by a quick oven dry at for 3 minutes.The mineral dyeing was stable to hot water washings and no evidence offabric tendering could be detected by hand breaking. Samples of the dyedfabric, before and after water washing, were X-ray fluorescence analyzedfor copper, manganese, and zirconium:

Percent Sample Mn Zr Cu Before wash 0. 44 3. 03. 0. 19 After wash 0. 453. 07 0. 15

The fungicidal copper, manganese, zirconium mineral dyeing was stable towashing with hot water.

EXAMPLE 13 Demonstrates the incorporation of phenylmercur'icacetate-zirconyl ammonium carbonate (B) stock into a manganese-free ironbath for bright orange mineral dyeing with fungicide.

Orange mineral dye bath w/fnngicide 50.00

Bath is orange brown in color and clear. It contains 0.39% mercury asmetal. A section of scoured duck 8" x 9" was wetted with the bath,blotted free of excess liquid, and oven dried at 100 C. for 4 minutes,followed by a cure of 105 C. for 1 minute. A bright orange mineraldyeing resulted, having a fungicidal phenylmercury content. A section ofthe cured fabric was washed with hot running tap water for minutes,followed by oven drying at 130 C. for 3 minutes. The dyeing was stableto hot water washing. Mercury analyses before and after wash showed0.26% before and 0.21% after wash.

EXAMPLE 14 Repetition of Example 13 using ferric chloride FeCl -6H ODemonstrates the incorporation of the copper metaborate-zirconylammonium carbonate with an iron-ammonium oxalate bath, withoutmanganese, for bright orange copper-based fungicidal mineral dyeingsfrom a single bath.

Ferric chloride (FeCl -6H O) 2.00 Water (distilled) 40.00

Ammonium oxalate (NH C O -H O 3.00 Zirconyl ammonium carbonate-coppermetaborate (A) stock (Example 11) 5.00

Bright orange fungicidal dye bath 50.00

A clear coffee brown colored bath solution is produced, and thiscontains 0.32% copper as metal and 0.39% zirconium as ZrO A section ofscoured duck 8"x9 was Wetted with the bath, blotted free of excessliquid, and oven dry-cured at 100 C. for 6 minutes. A bright orange(fungicidal) mineral dyeing resulted, having a theoretical coppercontent of approximately 0.2% (Cu). The dye color shade was comparableto the color shade produced in Example 7, Where no fungicide wasincorporated. Tensile breaking strength showed approximately 90%95%retained strength after treatment. Copper analyses weer made before andafter 10 minute hot tap water wash:

Sample: Percent copper (Cu) Before wash 0.17 After wash 0.13

The color shade was also stable to hot tap water washing.

EXAMPLE 16 Demonstrates the acid oxalic tendering effect withpermanganate baths with excess ammonium oxalate.

Potassium permanganate (KMnO 1.00 Water (distilled) 25.00

Bath (brown) 27.00

Bath (A) contains approximately 0.247 g. potassium and 0.63 g. oxalicacid. Bath (B) contains 0.247 g. potassium and 0.315 g. of oxalic acid.When both baths are applied to scoured duck 8" x 9", and both treatedfabrics cured at 130 C./5 minutes, the fabric treated with (A) shows 44%strength loss (tensile strength), while the fabric treated with (B)shows only 29.0% strength loss. Excess oxalic acid increases oxidativedegradation.

EXAMPLE l7 Demonstrates several color shade bath systems, usingmanganese and iron with zirconia:

5993-134-II (Manganese-zirconia) Orange-brown mineral dye bath (0.35 Mn)50.00

5993-III (Manganese, iron and zirconia) G. Potassium permanganate (KMnO0.50 Ferric sulphate (Fe (SO -xH O) 1.00 Ammonium oxalate (NH C O -H O1.00 Zirconyl ammonium carbonate (10% ZrO 5.00 Water (distilled) 42.50

Light brownish orange mineral dye bath (0.35%

5993-125-IV (manganese, iron, and zirconia) (low Mn) G. Potassiumpermanganate (KMnO 0.25 Ferric sulphate (Fe (SO 'xH O) 1.00 Ammoniumoxalate (NH C O -H O 1.50 Zirconyl ammonium carbonate (10% ZrO 5.00Water (distilled) 4225 Light orange (brownish) mineral dye bath (0.17%

5993-124-V (iron and zirconia) G. Ferric sulphate (Fe (SO -xH O) 2.00Ammonium oxalate (NI-I C O -H O 3.00 Water (distilled) 40.00 Zirconylammonium carbonate (10% ZrO 5.00

Bright orange mineral dye bath (0% Mn) 50 .00

5993-124-VI (manganese, iron, and zirconia) fluorescence analyses formanganese, iron, and zirconium G. percentages: Potassium permanganate(KMnO' 0.50

BEFORE WASHING Ferric sulphate (Fe (SO -xH O) 2.00 Ammonium oxalate(NI-I C O -H O 3.00 5 Percent Water (distilled) 39.50 Manga- I Zirco-11650 I011 mum Zirconyl ammomum carbonate ZrO 5.00 sample Number ColorShade (Mn) (Fe) (Zr) 599343441 R dd h-b 0. 49 0.05 2.01 Mediumorange-brown mineral dye bath (0.35% 5993 136 I M1 0.06 280 Mn) 50.00Orange-brown 0.14 0.15 2. 79 Light brownish-orange 0.16 0. 28 2. 005993136III (manganese, iron, and zirconia) g 10 35 2 11 G Bright orange0.002 0.66 2.33 P KM O 1 lltgedium orange-brown. $4 58 g otags erm nanal; eep orangerown 9 .1 Ferric gfi g zi 85 6 2 599 -137-II B ht a 00030.69 4.03 Ammonium oxalate (NH C O -H O 0.50 15 Water (distilled) 43.25Zirconyl ammonium carbonate (10% ZrO 5.00

Deep orange-brown mineral dye bath (0.7% Mn) 50.00

5993-137-II 1 (iron and zirconia) G. Ferric chloride (FeC1 -6H O) 2.00Ammonium oxalate (NH C O -H O 3.00 Water (distilled) 35.00 Zirconylammonium carbonate (10% ZrO 10.00

acid fabric tendering, increase the color shade brightness, and add tolight screening, and algaecidal properties.

EXAMPLE 18 Demonstrates the application of the color shade baths ofExample 17 to scoured duck: Each of the nine baths so prepared were usedto wet two 9" x 12" sections of scoured 10 oz. duck. The untreated duckwas thoroughly wetted with the bath, blotted free of excess liquid, andoven dried at 90 C. for 5 minutes, followed by an oven cure of 100 C.for 2 minutes, when the respective mineral dye was completely deposited,with the respective color shade being obtained. The cured samples wereallowed to cool under room conditions (25 C.) for one hour. The mineraldyeings were designated at follows:

5993-13441 Reddish-brown.

5993-125-I Orange-brown. 5993125-III Light brownish-orange. 5993-125-IVLight orange. 5993-124-V Bright orange. 5993-124-VI Medium orange-brown.5993-136-III Deep orange-brown. 5993-13741 Bright orange.

The color shade range is between orange and brown.

EXAMPLE 19 One each of the treated samples prepared in Example 18 weredesignated for washing, and were subjected to a wash of running hot tapwater (55 C.) for a period of 10 minutes. The washed samples were thenremoved, blotted free of excess water, and oven dried at 130 C. for 3minutes. The color was compared with the unwashed respective samples. Inevery instance, the color was negligibly affected, and the washedcolored fabrics were comparable to the corresponding unwashed coloredfabrics, showing the mineral dyeings to be stable to hot water washing.

EXAMPLE 20 Samples of the mineral dyed fabrics before washing, and thecorresponding mineral dyed fabrics after 10minutes hot tap waterwashing, were submitted for X-ray During washing, the color shades arestable and only surface deposits were removed, as evidenced by X-rayfluorescence analyses with the washed samples:

AFTE R WASHIN G Percent Manga- Zirconese Iron nium Sample number Colorshade (Mn) (Fe) (Zr) 5993-13 9110 Reddish-brown 0. 42 0. 05 1. 965903-136-IW do 0. 47 0. 05 2. 67 5093125IW Orange-brown 0. 14 0. 14 2.50 5993125Il'IW.. Light brownish-orange 0.12 0. 26 1. 96 5093-125-1VWLight orange- 0. 09 0. 28 1. 69

5993-121-VW Bright orange..- 0. 002 0. 1. 7 5095-124-V1W Mediumorange-browm 0. 12 0. 49 1. 80 )3126I1I. Deep orange-brown 0. 25 0.08 1. 92 5903-137-11 Bright orange 0.002 0. 58 3. 97

The residual manganese, iron, and zirconium add-ons, after washing, arewell above theory for wet pickup, demonstrating good hot water washresistance and retention of mineral dye pigment (color).

EXAMPLE 21 Sections of cured and unwashed mineral dyed scoured ducksamples were tested for tensile breaking strength to determine theeifect of the treatment on the fabric in heat curing. The results arereflected in the following results:

Tensile strength retention Was high in all formulations where manganese(permanganate) was less than 0.3% as Mn add-on. The high iron (orange)and less than 0.3% manganese to 0% Mn, orange to brownish-orange shadesof mineral dyed fabrics showed 86% to 99% retained tensile strengthvalues.

EXAMPLE 22 Demonstrates the tendency of permanganate to reduce thefabric strength through oxidation in heat curing without ammoniumoxalate or subsequent oxalic acid degradation. The followingformulations were prepared and applied to scoured duck:

G. Potassium permanganate (KMnO 1.00 Water (distilled) 31.00

Bath for (Bistic) Manganese Brown (1% Mn) 32.00

Two samples of duck were wetted with the bath, blotted free of excessliquid, and cured as follows:

(1) one sample at C./3 minutes followed by C. for 2 minutes.

13 (2) one sample at 100 C./6 minutes (dry-cure).

Sample (1) showed a 40% fabric strength (tensile) loss, and sample (2)showed a 40% fabric strength (tensile) loss, showing that permanganatealone causes fabric degradation by oxidation in heat curing without acid(oxalic). Degradation is relative to the amount of permanganate(oxidation) present in the bath, and not temperature.

G. Potassium permanganate (KMnO 1.00 Water (distilled) 26.00 Zirconylammonium carbonate ZrO 5.00

Reddish-brown dye bath (1% Mn) 32.00

Two samples of duck were wetted with bath, blotted free of excessliquid, and cured as follows:

( 1) one sample at 130 C./ 3 minutes followed by 140 C. for 2 minutes.(2) one sample at 100 C./ 6 minutes (dry-cure).

14 since iron oxide deposition from this process does not demonstratesignificant fabric degradation.

I claim:

1. A pad bath formulation, said bath consisting of about 1 to 4 parts ofan iron salt, selected from the group consisting of ferric chloride andferric sulphate, about 0.5 to 3.7 parts of potassium permanganate, about1 to 6 parts of ammonium oxalate, about to parts of water, and about 10to 20 parts of a zirconyl ammonium carbonate solution containing about10 weight percent zirconium dioxide.

2. A pad bath formulation prepared according to the process of claim 1wherein the iron salt is ferric chloride.

3. A pad bath formulation prepared according to the process of claim 1wherein the iron salt is ferric sulphate.

References Cited UNITED STATES PATENTS 3,394,027 7/1968 Conner et a1...117-138.5 2,923,592 2/ 1960 Crosland 8-52 3,291,635 12/1966 Conner117-143 X 3,431,059 3/ 1969 Conner et a1. 8-52 3,183,118 5/1965 Conner117-1385 3,446,656 5/1969 Conner 117-1385 GEORGE F. LESMES, PrimaryExaminer P. C. IVES, Assistant Examiner US. Cl. X.R.

